Making antiknocking motor fuel and synthetic resins



Patented May 11, 1937 UNITED STATES MAKI I VG ANTIKNOCKING MOTOR FUELAND SYNTHETIC BESINS Carleton Ellis, Montclair, N. 1., assignor'toEllis- Foster Company, a corporation of New Jersey No. Drawing.

Claim.

This invention relatesto the process of making motor fuel and by-productpetroleum derivatives.

The invention relates especially to motor fuels made from'heavy.pe'troleum oils by heating in the presence of air thus obtainingcertain oxidized bodies along with products of cracking, capable ofreducing detonation or knocking in internal combustion engines.

The invention has for one object the productiorl of so-calledanti-knocking motor fuels which do not require any addition of specialanti-knock chemicals such as lead tetraethyl or other substancesrecognized to have poisonous properties.

In the air-treatment of heavy oils certain byproducts, principally'acidsand aldehydes are produced, giving the raw fuel and objectionable odor.

Refining with sulphuric acid and caustic soda in the usual way and inthe customary proportions does not deodorize satisfactorily. If a largeamount of sulphuric acid is employed excessivelosses occur due to attackof the acid on olefins, aldehydes and the like.

The organic acid products higher than acetic acid, such as butyric,valeric, capric, caprolc and the like have rather 'oflensive .odors.However since these acids have "a commercial value for other purposes Ipropose to remove or .collect them by absorbing in or washing with analkalized in various ways.

line solution thereby obtaining the salts of the several organic acids.Such salts may be utier aldehydes possess vile penetrating odors in somecases not without lachrymatory or tear-producing properties, I prefer toeliminate practically all traces of such evil-smelling. aldehydes fromthe motor fuel.

Procedures which I propose for the purpose are:

(1) Hydrogenation of the raw motor fuel or the fuel after washing withalkali to remove sulphur containing bodies, or

(2) Conversion of aldehydes to polymers either capable of extraction orfree from ofl'ensive odor, or

(3) Addition of phenol or other phenolic body simple Application March30, 1925, Serial No. 19,538

to the raw motor fuel or any desired fractions thereof andcausingreaction to take place in alkaline or acid medium to produce syntheticresins.

The oxidation of the petroleum oil or fractions thereof may be carriedout either in the liquid phase or the vapor phase. In the former casethe charge of oil is preferably placed in a" pressure tank and heated toa temperature of 500 F. or thereabouts air being blown in and a pressuremaintained preferably of approximately 20-30 atmospheres. In the vaporphase a distillate in the vapor form from a still such as a crackingstill is admixed with air and passed through a reaction zone whichpreferably contains a catalyzer to yield the partially oxidized -motorfuel and acid and aldehy'dic by-products.

The distillate by either. procedure consists of two portions, namely anoily layer containing the naphtha and burning oil components (gasolineand kerosene fractions) in a more or less oxidized condition, someheavier oils and oxygenated by-products soluble in oil includingaldehydes especially higher aldehydes and various fatty acids and thelike.

Beneath the oily layer is an aqueous layer containing acetaldehyde andotheraldehydes soluble to some extent in water, various lower organic.acids soluble in water and so forth. 'Ihe various substances, both oiland water-soluble, will be' distributed between the two layers inproportion to their respective coeilicients of partition.

It is proposed to treat the distillate or any appropriate part thereofat any suitable stage of the process, with phenol or cresol or otherappropriate phenolic body using, for example, a proportion sufficient tocombine with-the aldehydes present on the basis of a moi. of phenol to amoLof aldehyde or preferably using excess of the phenolic body. 1 asuchtreatment may be carried out in various ways. For examplethe phenolmay be added to the hot vapors coming from the still or this substancemay be fed slowly into the still itself or into the vapor dome thereof.The phenol may be applied in a liquidform or may be first vaporized. Theproportions employed as indicated preferably are those which correspondroughly to the aldehyde formation preferably however employing an excessof phenol in order to obtain a moderate a fusible resinous product. Withan excess of be readily utilized for many purposes available to thefusible product.

Under the high pressure and temperature in the still or in thecondensing apparatus or receivers and in' the presence of organic acidsformed during the oxidation acting as catalysts combination takes placebetween the phenpl and aldehydes and resinification ensues. When sulphuris present in the raw oil this usually is oxidized to sulphur dioxideand the latter acts as a catalyzer.

Or the phenol may be added to the condensate at any suitable stageduring the condensation of said distillate or added to the liquidcollecting in the receiver. When condensation is carried out .underpressure and the liquid therein is warm the addition of phenol to thecontents may readily bring about resinification therein. When thecondensate is at atmospheric pressure the phenol may be brought intoreaction with the aldehydes by heating under a reflux condenser in thepresence of anacid or alkaline condensing agent.

Or the water layer and the oily layer may be separated and phenol addedseparately to either one or the other or to both of these separatedproducts; in which case resins are obtained from the water layer whichare different from those resulting from resinification in the oilylayer.

When reaction is carried out separately it is desirable in some cases towash the oily layer with water and addthe washings to the aqueous layer.

Any suitable fractions of the oily layer may be treated in this mannerand also concentrates or distillates obtained by boiling the waterlayer, to obtain a mixture of aldehydes, acids and so forth admixed withsome water. By neutralizing with alkali the organic acids may beretained.

When the oily layer is first distilled before removing aldehydes byresinification it may previously be treated with caustic soda to retainany organic acids in the form of their sodium salts. When phenol ispresent under these conditions, especially when the solution is alkalineresin remains in the residue. The latter may be steam stilled or vacuumstilled to remove heavy oils and the like when these are present. Thisprocedure may not be necessary when low boiling fractions only are used.If an excess of phenol has been employed it may be recovered by steamdistillation.

The separation of the resin from the water layer is simpler since duringresinification coagulation of the resin occurs and the latter may becollected by filtration or decantation. If however a large proportion ofalkali is employed the resin may remain in solution. Made in slightlyalkaline solution the coagulated resin may be washed to remove salts oforganic acids and may be further modified by reaction with othersubstances such as formaldehyde, 'acetaldehyde, paraldehyde, furfuraland hexamethylenetetramine and so forth; also by adding natural resinssuch as asphalt, copal, shellac or substances such as rubber, wax,nitrocellulose and the like.

If the resin is too soft for making varnishes or other coatingcompositions or for plastic molding purposes it may be steam stilled orvacuum stilled or hardened by heating.

When incorporated with the various fillers used in the plastic industrymolding compositions may be made which set or cure in the mold on hotpressing. Such compositions may contain a few per cent ofhexamethylenetetramine.

The varnishes obtained by dissolving the resin in for example a mixtureof alcohol and benzol maybe used to impregnate paper, cloth or othersubstances which in turn may be pressed together to yield laminatedpressboard, gear blanks and the like.

A considerable choice of catalysts is available carrying out theresinification process which constitutes a step in the refiningoperation. As noted above organic acids and sulphur dioxide are likelyto be present and these are in most cases appropriate for bringing aboutthe reaction with the phenolic body. If not however mineral acids suchas sulphuric, hydrochloric or phosphoric acids may be introduced. Incase acid resinification is not complete it may be followed by treatmentwith alkali to advantage.

In some cases the resinificatlon may form a part of the usual refiningprocess employing sulphuric acid and then caustic soda, the acidtreatment coming first. In other cases the materials to be refined mayfirst be rendered alkaline in order to obtain the resin in the absenceof acid. Again the materials may be neutralized and the phenolic bodyadded.

Thus it is possible to add phenol to the oil and introduce sulphuricacid in the usual refining proportions, agitate and maintain warm untilresin forms and passes into the sludge. The latter is then neutralizedand washed. The neutralizing may be carried out in some cases by meansof barium or calcium hydroxide. The sulphate which thus forms may beutilized as a filler along with the resin. 01 the sulphuric acid mayfirst be added and the phenol introduced slowly. In accordance witheither .of the foregoing steps it is also possible to obtain asuphonated resin which may be used as a tanning agent in the leatherindustry.

Again it is possible to first treat with sulphuric acid, remove thesludge and then add the phenolic body and a further quantity of an acidsuch as hydrochloric acid. Also it is possible to first treat withsulphuric acid, then with or without removal of the sludge, add phenoland caustic soda produced by the oxidation of the petroleum oil or maybe present in the original oil and may be distilled off unchanged,allowance should be made for such phenoloid substances when addingphenolic bodies from extraneous sources.

The naphthas and burning oildistillates may be appropriately separatedand steam stilled if desired to obtain fractions having a narrow rangeof boiling point. Ordinarily the lower fractions are employed as motorfuel and these preferably should contain as much of the burning oildistillate or kerosene as is feasible. Since the oxidation procedureyields a fuel which has'a less tendency to detonate in an internalcombustion engine it is proposed to use a higher proportion ofoutside ofthe scope of the present invention. The motor fuel obtained as above maybe blended with .pressure still naphtha, ordinary gasoline, casingheadnaphtha and the like employing for example equal parts of'the oxidizedmotor fuel and the naphtha from,other sources; or these proportions maybe varied in various ways for example from 25 per cent of one product to'75 per cent of the other. The present invention comprehends suchblended products, that is oxidized motor fuel admixed with motor fuelsof a normally unoxidized'character such as the naphthas aforesaid aswell as additions such as aniline, pyridine, benzol and the like tendingto assist in reducing detonation or eliminating it entirely.

In the foregoing I have referred to aldehydes and organic acids as beingimportant by-products of the present process. It should be understoodthat there are certain compounds known as aldehyde acids which containboth the aldehyde and acid group and whichI preferably do not form inthe process and which would :be disturbing factors if combining withphenol to make certain resins. I prefer ordinarily to conduct theprocess to make normal aldehydes not containing any acidic grouping.However when aldehyde acids are formed these may be removed if desiredalong with normal organic acids by treatment with an alkali wash.

The fol-iowing illustrates onemethod of carrying out vapor phaseoxidation but it should be understood that I do not wish to be limitedto the details of such description.

A catalyst was prepared by treating rough fragments of iron possiblyone-eighth to onefourth of an inch in diameter with a solution ofammonium metavanadate. The salt was dissolved in boiling water and thesolution evaporated in contact with the iron fragments stirring gently.In this way a crystalline incrustation on the surface of the ironfragments was obtained. It may be added that the solution was keptalkaline during evaporation by the addition of aqueous ammoniumhydroxide. This material was placed in the catalytic apparatus andignited in a stream of air at between 200 and 250 C. In another casevanadium pentoxide was suspended in a one per cent solution of solublecotton in acetone and a mixture allowed to dry in contact with fragmentsof iron. The mixture was used in such proportions that 20 grams ofvanadium pentoxide were applied to 18 grams of iron. On evaporation acoating of the vanadium oxide on the iron fragments was obtained. Thismaterial could be handled to better advantage than thematerial mentionedabove having a crystalline coating and on ignition in the catalyticapparatus yielded a catalyst which was somewhat more permanent, that isthe coating of vanadium material did not appear to dislodge so easily.

ErampleP-Allow 300 parts of kerosene to drip into a cracking furnacemaintained at a tem perature of 1200-1300 F. The vapors of the crackedkerosene are passed through an aircooled condenser where the higherboilingconstituents are condensed and collected. The lighter material ispassed on to the mixing chamber consisting of a Venturi tube to bemixed. with air. The mixture of air and cracked kerosene vapor is passedinto a catalytic chamber containingcatalyzer consisting of fragments ofiron coated with 10 per cent of its weight of vanadium oxide. Thecatalytic chamber is heated by means of the lead bath maintained at thedesired temperature, namely 800-1000 F. by meansof anelectrically-heated coil. The temperature of the exit gases variesbetween 455 and 750 F.. The liquid products of the oxidation of thepetroleum vapor are collected by condensation and washing. React uponthe aldehydic co" stituents with phee nol as aforesaid to form resinswhich are readily separable from the other products.

The following illustrates the procedure of oxidation in the liquid phasebut it should likewise be understood that the invention is not limitedto the particular temperatures, pressures and other details set forthfor illustrative purposes.

Example-Heat a body of gas oil to about 500 F. in a still adapted towithstand a pressure of well over 20 atmospheres. By means of a pressurepump force air at 15-20 atmospheres into the body of oil in the lowerpart so that the air passes up through a deep column of the oil in theform of small bubbles thus coming in.

intimate contact with the oily material. The air is preheated to between200 and 300 F. Allow the products from the still to pass into acondenser which should likewise be capable of withstanding highpressures. The walls of the condenser may be made of copper to avoidattack by acids which would result if steel were employed. Allow thetemperature to rise spontaneously by the action of the air on the oil.Regulation may be effected by adjusting the temperature of the incomingair or the rate at which it passes through the oil. Oil may be fedcontinuously into the receptacle in the upper part and the residues maybe continuously withdrawn from the lower part. The condensate obtainedconsists of two layers, an upper one containing the hydrocarbons andoxidized products insoluble in water and the lower layer'containingacids, aldehydes and other substances. Wash the hydrocarbon layer withwater and add the washings to the aqueous layer. Distill thewaterinsoluble layer to make fractions appropriate as a motor fuel forexample fractions boiling within the range of ordinary gasoline orslightly higher. Make the aqueous layer slightly acid with 2 or 3 percent of sulphuric acid and'add phenol somewhat in excess of the amountrequired to resinify the aldehydic substances present. This may bedetermined approximately by preliminary test on.

the small scale. Filter off the resin and remove tion. The resin maythen be dissolved in a mixture of equal parts of benzol and denaturedalcohol in the proportion of one pound of resin to one or two pounds ofthe solvent mixture. Hexamethylenetetramine may be added and thesolution employed to impregnate wood flour or other filler to makemolding composition or to impregnate sheets of paper which aresubsequently hot pressed to obtain laminated pressboard. Or the resinmay be ground in a ball mill with asbestos, wood flour or other fillerand 5 to per cent of hexamethylenetetramine. This mixture is then passedthrough hot milling rolls and is finally ground to yield a moldingcomposition.

In the last described procedure there is no need of a fire under thestill hence the risk of overheating a still bottom is' obviated. Thus itis, possible to employ pressures in excess of 30 atmospheres. Thus itbecomes possible to oxidize the less heavy oils such as kerosene oreasily sublimable substances such as naphthalene at pressures of 50 to150 atmospheres. Still higher pressures for example 200 to 300atmospheres also are contemplated. To apply such super-abnormalpressures to an ordinary direct fired still the bottom of which whencoked may reach the temperature at which steel softens, would be out ofquestion. The present invention however makes such super-abnormalpressures utilizable with accompanying compactness of still andcondensation apparatus and with the possibility of securing peculiar andspecific oxidation effects at pressures above 35 atmospheres.

When treating a comparatively volatile substance at super-abnormalpressures (e. g. above 35 atmospheres) thestill may be started with aheavy oil and the more volatile substance gradually fed in, thesuper-abnormal pressure applied being that giving the most desirableoxygen relationship (ratio of oxygen to charge in the still at any giventime) for the purpose in hand.

Super-abnormal pressures make possible a great Lil variation in thisoxygen relationship with consequent specific oxidizing effects. Theinvention thus embraces a process of oxidation which comprises bringingan oxygen containing gas, preferably air, into intimate contact with anoxidizable organic body in a heated state at super-abnormal pressures,preferably in excess of 35 atmospheres; said organic body being, forinstance, a readilyvolatile hydrocarbon preferably at least'in part in aliquid condition while in the oxidizing chamber.

Example-Carry out the method described under the second example treatingkerosene at a pressure of atmospheres and a temperature between 750 F.and 950 F. v

The employment of super-abnormal or supercracking pressures ranging from35 atmospheres to 200 atmospheres or higher is not restricted to thetreatment of lighter oils such as kerosene or xylol but may be appliedto the super-cracking oxidation of coal tar and its distillates, shaleoil, pitches, asphalts, bituminous coals, petroleum residues and tars,vegetable oils and other glycerides and their fatty acids. which areliquid or are liquefied by heating are best adapted for theheat-and-pressure oxidation treatment.

The process especially when conducted at super-cracking pressures may becarried out by causing the oil to flow along the lower half of a longpipe, slightly inclined from the horizontal, and allowing the air tomove in counter-current manner in the upper portion of the pipe. Thispermits air of highest oxygen content to first contact with the residuesof oxidation. The pipe may be cooled t any. zones of too intensereaction.

In lieu of applying external cooling, when overheating is observed incarrying out any of the above procedures, the air may be diluted withthe nitrogen and other waste gases of the operation, or steam may beintroduced along with the air. On the other hand the enrichment of airby adding oxygen, or gases richer in oxygen than is air, is notprecluded.

What I claim is:--

1. The process which comprises treating hydrocarbon oils containingsulphur to produce motor fuel constituents containing aldehydes andsulphur dioxide, and removing the aldehydes by resinification withphenols in the presence of the sulphur dioxide.

2. The process which .oniprises subjecting heavy oils to a crackingtemperature in the pres- Organic substances ence of air, whereby lighthydrocarbon motor fuel constituents and normal aldehydes are formed, andreacting on the aldehyde-containing motor fuel constituents with aphenol in the presence of a catalyst, whereby resins result, andseparating the resins from the motor fuel constituents.

3. The process which comprises subjecting heavy oils to a crackingtemperature in the presence of air, whereby light hydrocarbon motor fuelconstituents and normal aldehydes are formed, and reacting on someportion at least of the aldehyde-containing product with a phenol in thepresence of a catalyst, whereby resins result.

4. The process which comprises treating hydrocarbon oils to producetherefrom light hydrocarbon motor fuel constituents containing aldehydesand organic acids, and removing the aldehydes by resinification withphenols in the presence of said acids.

5. The process which comprises treating hydrocarbon oils to producetherefrom light hydrocarbon motor fuel constituents containing aldehydesand acidic oxidation products, and removing the aldehydes byresinification with phenols in the presence of said acidic oxidationproducts.

6. The process of producing motor fuel components which comprisessubjecting a heavy hydrocarbon oil to a cracking temperature in thepresence of air whereby light hydrocarbon motor fuel constituents andaldehydes are formed, removing the aldehydes by resinification, andrecovering the substantially non-aldehydic light hydrocarbon motor fuelconstituents.

7. The process of partially oxidizing heavy oils which comprisesbringing air into intimate contact with a heavy hydrocarbon oil in aheated state under pressures exceeding 35 atmospheres under conditionsto produce light hydrocarbon motor fuel constituents and volatileoxygen-containing compounds, and recovering the light hydrocarbon motorfuel constituents.

8. The process of partially oxidizing heavy oils which comprisesbringing air into intimate contact with a liquid oxidizable organic bodyin a heated state under pressures exceeding 35 atmospheres underconditions to produce volatile oxygen-containing compounds and otherorganic derivatives, and recovering the volatile oxygencontainingorganic compounds.

9. The process which comprises subjecting heavy oils to a crackingtemperature in the presence of air under pressures exceeding 35atmospheres, whereby light hydrocarbon motor fuel constituents andnormal aldehydes are formed, and reacting on the aldehyde-containingmotor fuel constituents with a phenol in the presence of a catalystwhereby resins result, and separating

